1. Field of the Invention
The present invention relates to novel diol compounds each having a comb-shaped structure, novel water-soluble polyurethane obtained using thereof, and usages of the water-soluble polyurethane.
The present invention also relates to an extruding auxiliary using the above novel water-soluble polyurethane, an extruding composition of a cement material containing the extruding auxiliary, and extruded articles of a cement material having improved strength obtained by extruding the above extruding composition of a cement material. The present invention further relates to a novel thickening agent for a mortar available for widely varying types of mortar such as repairing mortar, tile-bonding mortar, masonry mortar, spraying mortar, substrate mortar and topping mortar. The present invention further relates to a novel thickening agent for an underwater concrete and a composition for at underwater concrete containing the novel thickening agent for an underwater concrete. The present invention further relates to a novel ceramics forming binder. And the present invention further relates to a novel moisturizer for hair cosmetics excellent in moisture retention to hair.
2. Related Arts
When extruding a mortar comprising a cement, a fine aggregate, a fiber and water with a vacuum extruder or the like to produce cement plates extruding the same, in order to extrude the mortar without separating water therefrom, in other words, in order to impart water retention to the mortar, there has been a need to add a water-soluble polymer to the mortar (refer to, for example, Japanese Patent Publication No. 43-7134). In order to develop sufficient water retention, the aqueous mortar solution needs to have a high viscosity, and water-soluble cellulose ethers such as methyl cellulose (MC), hydroxypropyl methyl cellulose (HPMC) and hydroxyethyl cellulose (HEC) are mainly used as the water-soluble polymer at present.
In order to retain the shape of extruded articles immediately after extrusion, in other words, in order to impart shape retention to mortar, the mortar needs to exhibit excellent thixotropic properties; and, it was not sufficient to impart shape retention thereto by an addition of only the water-soluble polymer such as methyl cellulose to the mortar. Thus, asbestos has been used in combination with water-soluble cellulose ethers (refer to, for example, Japanese Patent Publication No. 43-7134).
So, in the conventional extrusion process, the requirements of water retention and shape retention of mortar in extruding mortar have been satisfied by the use of asbestos in combination with water-soluble cellulose ethers.
In recent years, however, the harmfulness of asbestos has been pointed out and restrictions have been imposed on its use. As a result, the fibers such as various types of polymer fibers and glass fibers have become in use as substitutes for asbestos. The mortar using these asbestos-substitute fibers is, however, inferior in shape retention to the mortar using asbestos. Thus, there have been demands for the development of novel extruding auxiliary capable of imparting water retention as well as sufficient shape retention to mortar with the use of asbestos-substitute fibers.
On the other hand, the water-soluble cellulose ethers have a problem that they are likely to trap bubbles when mixing mortar, and due to the bubbles, the strength of the extruded articles of the mortar is likely to decrease.
In addition, the water-soluble cellulose ethers are relatively expensive because they are semisynthetic polymers produced from special natural wood pulp as a raw material and boost the raw material costs of the extruded articles. Furthermore, the natural wood pulp as resources is limited. Thus, a novel extruding auxiliary has been desired which can be synthesized from less expensive industrial materials.
In the forming of ceramics, particularly in extrusion of ceramics, an extruding binder composed of a water-soluble polymer is blended so as to impart sufficient plasticity, tackiness and lubricating properties to the green sand, and various types of cellulose ethers such as methyl cellulose (MC) and hydroxypropyl methyl cellulose (HPMC) are widely used as the polymers.
The cellulose ethers, however, have a problem that their heat release in degreasing is rapid and the heat release value is high, therefore, the extruded articles are likely to be damaged at the time of degreasing. Furthermore, it is also a problem that carbonized residues or carbonized inorganic salts are likely to remain after degreasing (high carbon residue content).
Hair cosmetics such as hair conditioner, hair gel, hair foam, shampoo and rinse require moisturizer, which contains water-soluble polymer, so as to create moist feel. And, as the polymers for such cosmetics, water-soluble polymers such as polyethylene glycol (PEG) or various types of cellulose ethers are widely used at present.
However, for polyethylene glycol, it has a problem of creating a sticky hair impression, but not creating moist feel. At the same time, cellulose ethers such as hydroxyethyl cellulose (HEC) also have a problem of creating a stiffed hair impression, but not creating moist feel.
Accordingly, an object of the present invention is to provide novel diol compounds each having a comb-shaped structure and novel water-soluble polyurethane using thereof.
Another object of the present invention is to provide a novel extruding auxiliary as a replacement of water-soluble cellulose ethers, and which is more economical and is capable of imparting excellent shape retention to mortar, imparting excellent strength to the extruded articles of the mortar, and imparting improved formability to mortar. Still another object of the present invention is to provide an extruding composition of cement-based material which has excellent shape retention, of which extruded articles have excellent strength, and of which formability has been improved, and extruded articles of cement-based material of which strength has been improved.
Still another object of the present invention is to provide a novel mortar thickening agent which is available for widely varying types of mortar such as repairing mortar, tile-bonding mortar, masonry mortar, spraying mortar, bedding mortar and facing mortar.
Further object of the present invention is to provide a novel thickening agent for underwater concrete as a replacement of water-soluble cellulose ethers, and which is more economical and excellent in underwater anti-separating properties, and is improved retardation of setting.
Still further object of the present invention is to provide a novel ceramics forming binder to replace cellulose ethers whose heat release in degreasing is slow, heat release value is low, and carbon residue content is also low.
Yet another object of the present invention is to provide a novel moisturizer for a hair cosmetic as a replacement of PEG or cellulose ethers, and which imparts water retention to hair and creates excellent moist hair impression.
After concentrating our energies on solving the aforedescribed problems, we, the present inventors found that the above-described properties such as water retention and formability can be attained by improving the structure of comb-shaped diol as a raw material of water-soluble polyurethane, and on the basis of this acknowlegement we finally thought out the present invention.
Specifically, the present invention with which the above objects can be achieved is a comb-shaped diol represented by the following general formula (1): 
wherein R1 is a hydrocarbon group of 1 to 20 carbon atoms; each of R2 and R3 is a hydrocarbon group of 4 to 21 carbon atoms; some or all of the hydrogen atoms of the hydrocarbon groups R1, R2 and R3 may be substituted with fluorine, chlorine, bromine or iodine; R2 and R3 may be the same or different from each other; each of X, Xxe2x80x2 and Xxe2x80x3 is an alkylene group of 2 to 10 carbon atoms; X, Xxe2x80x2and Xxe2x80x3 may be the same or different from each other; some of the hydrogen atoms of the above alkylene group may be substituted with an alkyl group, chlorine or an alkyl chloride group; each of Z and Zxe2x80x2 is oxygen, sulfur or a CH2 group; Z and Zxe2x80x2 may be the same or different from each other; R4 is an alkylene group of 2 to 10 carbon atoms in all; k is an integer of 0 to 15; n is an integer of 0 to 15 when Z is oxygen and is 0 when Z is sulfur or a CH2 group; nxe2x80x2 is an integer of 0 to 15 when Zxe2x80x2 is oxygen and is 0 when Zxe2x80x2 is sulfur or a CH2 group; and n and nxe2x80x2 may be the same or different from each other.
In an embodiment of the present invention, the comb-shaped diol includes a diol represented by the following general formula (1a): 
wherein R1 is a hydrocarbon group of 1 to 20 carbon atoms; each of R2 and R3 is a hydrocarbon group of 4 to 21 carbon atoms; some or all of the hydrogen atoms of the hydrocarbon groups R1, R2 and R3 may be substituted with fluorine, chlorine, bromine or iodine; R2 and R3 may be the same or different from each other; each of Y, Yxe2x80x2 and Yxe2x80x3 is hydrogen, a methyl group or a CH2Cl group; Y and Yxe2x80x2 may be the same or different from each other; each of Z and Zxe2x80x2 is oxygen, sulfur or a CH2 group; Z and Zxe2x80x2 may be the same or different from each other; R4 is an alkylene group of 2 to 4 carbon atoms in all; k is an integer of 0 to 15; n is an integer of 0 to 15 when Z is oxygen and is 0 when Z is sulfur or a CH2 group; nxe2x80x2 is an integer of 0 to 15 when Zxe2x80x2 is oxygen and is 0 when Zxe2x80x2 is sulfur or a CH2 group; and n and nxe2x80x2 may be the same or different from each other.
Further, in a preferred embodiment of the present invention, the comb-shaped diol includes a diol represented by the following general formula (2): 
wherein R1 is an alkyl group of 1 to 18 carbon atoms; each of R2xe2x80x2 and R3xe2x80x2 is a hydrocarbon group of 4 to 21 carbon atoms; R2xe2x80x2 and R3xe2x80x2 are the same; R4xe2x80x2 is a 1,2-ethylene group, 1,3-propylene group or 1,4-butylene group.
The present invention is also directed to a water-soluble polyurethane, which comprise a polymer having a repeating unit (U-1) represented by the following general formula (3): 
and a repeating unit (U-2) represented by the following general formula (4): 
wherein A is a bivalent group derived from a water-soluble polyalkylene polyol (hereinafter referred to as compound A), wherein the compound A having a general formula HOxe2x80x94Axe2x80x94OH, having hydroxyl groups at least on both terminals thereof and having a number average molecular weight of 400 to 100,000; B is a bivalent group derived from a polyisocyanate compound (hereinafter referred to as compound B), wherein the compound B being selected from the group consisting of polyisocyanates represented by a general formula OCNxe2x80x94Bxe2x80x94NCO and having 3 to 18 carbon atoms; and D is a bivalent group such that the compounds having a general formula HOxe2x80x94Dxe2x80x94OH is comb-shaped diol having the above-described general formula (1) (hereinafter referred to as compound D);
wherein the molar ratio of the repeating unit (U-1) being 0.5 or higher and 0.999 or lower, the molar ratio of the repeating unit (U-2) being 0.001 or higher and 0.5 or lower, the weight average molecular weight measured by the GPC being in the range of 10,000 to 10,000,000.
In a preferred embodiment of the water-soluble polyurethane according to the present invention, the molar ratio of the repeating unit (U-1) is 0.5 or higher and 0.99 or lower, the molar ratio of the repeating unit (U-2) is 0.01 or higher and 0.5 or lower, the above compound A is a polyethylene glycol of which number average molecular weight is 3,000 to 20,000, the above compound B is a diisocyanate compound selected from the group consisting of aliphatic diisocyanates of which total number of carbon atoms is 3 to 18, the above compound D is the comb-shaped diol having the above general formula (2), and the water-soluble polyurethane has a weight average molecular weight, as measured by GPC, being in the range of 100,000 to 1,000,000.
The present invention is also directed to the water-soluble polyurethane, wherein the above compound B is hexamethylene diisocyanate, isophoronediisocyanate, hydrogenated xylylenediisocyanate, hydrogenated tolylene diisocyanate, or norbornanediisocyanatomethyl.
The present invention with which the above objects can be achieved is further directed to an extruding auxiliary for a cement material, which comprises a water soluble polyurethane having a repeating unit (U-1) represented by the above described general formula (3) and a repeating unit (U-2) represented by the above described general formula (4), and wherein 2.5% aqueous solution of the polyurethane has a viscosity of 1,000 to 1,000,000 mPaxc2x7s.
The present invention is also directed to an extruding composition of a cement material which comprises hydraulic inorganic powder, fine aggregate, fiber, the above extruding auxiliary and water.
Further, the present invention is directed to the extruding composition of cement material wherein asbestos-substitute fiber is used as the fiber.
The present invention is also directed to an extruded article of cement material which is obtained by extruding the above extruding composition and thus having an improved strength.
The present invention with which the above objects can be achieved also directed to a mortar thickening agent which comprise a water-soluble polyurethane having a repeating unit (U-1) represented by the above-described general formula (3) and a repeating unit (U-2) represented by the above-described general formula (4), the molar ratio of the repeating unit (U-1) being 0.5 or higher and 0.99 or lower, the molar ratio of the repeating unit (U-2) being 0.01 or higher and 0.5 or lower, and wherein 2% aqueous solution of the polyurethane has a viscosity being in the range of 10 mPaxc2x7s to 300,000 mPaxc2x7s at 20xc2x0 C.
Further, the present invention is directed to the mortar thickening agent, wherein the above-described compound A, which is a constituent of the above-described polymer, is polyethylene glycol having a number average molecular weight being in the range of 1,000 to 20,000.
Still further, the present invention is directed to the mortar thickening agent, wherein the above-described compound B, which is a constituent of the above-described polymer, is a chain aliphatic diisocyanate or cyclic aliphatic diisocyanate.
In a preferred embodiment of the mortar thickening agent according to the present invention, the above-described compound B is hexamethylene diisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, or norbornanediisocyanatomethyl.
In another preferred embodiment of the mortar thickening agent according to the present invention, the above-described compound D is a comb-shaped diol represented by the above general formula (1a), and more preferably a comb-shaped diol represented by the above general formula (2).
The present invention is also directed to a dry mortar composition which comprises hydraulic inorganic powder and the above-described mortar thickening agent.
The present invention is also directed to a mortar composition which comprises hydraulic inorganic powder, water and the above mortar thickening agent.
Furthermore, the present invention with which the above objects can be achieved is directed a thickening agent for underwater concrete which comprises a water-soluble polyurethane having a repeating unit (U-1)represented by the above-described general formula (3) and a repeating unit (U-2) represented by the above-described general formula (4), the molar ratio of the repeating unit (U-1) being 0.5 or higher and 0.99 or lower, the molar ratio of the repeating unit (U-2) being 0.01 or higher and 0.5 or lower, and wherein the polyurethane has a weight average molecular weight, as measured by the GPC, being in the range of 100,000 to 1,000,000.
In a preferred embodiment of the underwater concrete thickening agent according to the present invention, the compound D is a comb-shaped diol represented by the above general formula (1a), and more preferably a comb-shaped hydrophobic diol represented by the above general formula (2).
The present invention is also directed to the underwater concrete thickening agent, wherein the above-described compound B, which is a constituent of the above-described polymer, is chain aliphatic diisocyanate or cyclic aliphatic diisocyanate.
In a preferred embodiment of the underwater concrete thickening agent according to the present invention, the compound B is hexamethylene diisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, or norbornanediisocyanatomethyl.
In a preferred embodiment of the underwater concrete thickening agent according to the present invention, 2% aqueous solution of the water-soluble polyurethane has a viscosity being in the range of 1,000 mPaxc2x7s to 500,000 mPaxc2x7s.
The present invention with which the above objects can be achieved is also directed to an underwater concrete composition which comprises cement and the above underwater concrete thickening agent wherein the thickening agent is added at the rate of 0.1 to 10% by weight on the basis of 100% by weight of the cement.
The present invention is also directed to a ceramics forming binder which comprises a water-soluble polyurethane having a repeating unit (U-1) represented by the above-described general formula (3) and a repeating unit (U-2) represented by the above-described general formula (4), the molar ratio of the repeating unit (U-1) being 0.5 or higher and 0.99 or lower, the molar ratio of the repeating unit (U-2) being 0.01 or higher and 0.5 or lower, and wherein the polyurethane having a weight average molecular weight, as measured by the GPC, being in the range of 10,000 to 1,000,000.
In a preferred embodiment of ceramics forming binder according to the present invention, the compound D is a comb-shaped hydrophobic diol represented by the above general formula (1a), and more preferably a comb-shaped diol represented by the above general formula (2).
The present invention is also directed to the ceramics forming binder wherein the compound A, which is a constituent of the above-described polymer, is polyethylene glycol of which number average molecular weight is 1,000 to 20,000 and the compound B is a chain aliphatic diisocyanate or cyclic aliphatic diisocyanate.
In a preferred embodiment of ceramics forming binder according to the present invention, the compound B is hexamethylene diisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, or norbornanediisocyanatomethyl.
The ceramics forming binder of the present invention is preferably used as a binder for ceramics extrusion.
The present invention is also directed to a moisturizer for hair cosmetics which comprises a water-soluble polyurethane having a repeating unit (U-1) represented by the above-described general formula (3) and a repeating unit (U-2)represented by the above-described general formula (4), the molar ratio of the repeating unit (U-1) being 0.5 or higher and 0.99 or lower, the molar ratio of the repeating unit (U-2) being 0.01 or higher and 0.5 or lower, and the polyurethane having a weight average molecular weight, as measured by the GPC, being in the range of 10,000 to 1,000,000.
In a preferred embodiment of moisturizer for hair cosmetics according to the present invention, the above-described compound D is a comb-shaped diol represented by the above general formula (1a), and more preferably a comb-shaped diol represented by the above general formula (2).
The present invention is also directed to the moisturizer for hair cosmetics wherein the compound A, which is a constituent of the above-described polymer, is polyethylene glycol of which number average molecular weight is 400 to 20,000 and the compound B is a chain aliphatic diisocyanate or cyclic aliphatic diisocyanate.
In a preferred embodiment of moisturizer for use in hair cosmetics according to the present invention, the compound B is hexamethylene diisocyanate, isophoronediisocyanate, hydrogenated tolylenediisocyanate, hydrogenated xylylenediisocyanate, or norbornanediisocyanatomethyl.